DE3145714A1 - HEAT-CURABLE BINDING MIXTURE - Google Patents

Description

31457H 8

PAT 81 842 October 21, 1981

BASF Colors + Fibers Aktiengesellschaft, Hamburg

Thermosetting binder mixture 10

The invention relates to a thermosetting binder mixture based on organic resins.

Various chemical reactions have been proposed for curing by crosslinking the binders in paint films and also used. The chemical bonds formed during the crosslinking reaction are sufficient often not all of the requirements that are placed on the paint films. So are ester bonds Sensitive to hydrolysis, amine groups form hydrophilic impurities in the burned-in film.

With 2-component systems you often have to use one of the reactive Cap groups to prevent premature reaction.

For the priming of electrically conductive substrates, electrodeposition coating has been used in recent years found widespread use. So far, the focus has been on the anodic electrodeposition primer. the Resin binders used for this purpose belong to the carboxyl groups containing resins, e.g. to the maleinate oils, maleinized epoxy resins, alkyd resins, acrylic resins and especially to the maleinized polybutadienes. Salt formation, primarily with amines, made these resins water-soluble and attached to the anode deposited in the electrodeposition bath by the current. The anodic electrodeposition priming process contains each

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but serious disadvantages. During the electrodeposition process, oxygen is generated at the anode, which can seriously and disadvantageously alter the resins that deposit on the anode. Furthermore, metal ions, which are contained in the burned-in film as impurities, go into solution at the anode. The metal ions can cause discoloration and staining. In particular, they cause qualitative disadvantages by salt formation and thus by a reduction in water resistance and corrosion protection.

The cathodic electrodeposition priming process, which has been ready for the market in recent years, is displaced in increasingly the anodic process, since the deficiencies described above are largely avoided. So Hydrogen forms on the cathode, on which the paint film is now deposited, during the deposition process, which does not affect the resin binder. Since the cathodic deposition in the almost neutral pH range

can take place, hardly any metal ions go into solution.

The binders suitable for cathodic deposition predominantly contain amino groups that lead to Water solubilization can be neutralized with acids.

However, it is disadvantageous that the hydrophilic amino groups remain in the stoved film, which they cause a reduction in corrosion protection. By reacting the amino groups with blocked isocyanates When it came to networking, these were in the less than 30

hydrophilic urethane group, but at the same time the blocking agents, such as phenol or Ketoxime, released.

Depending on the type of constitution of the resin, necessarily 35

Amino groups contained in these can also be eliminated by ß-elimination are thermally split off (DE-OS 2 363 074, DE-OS 2 753 861). The resulting impurities

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generation of exhaust air through large quantities of the split off Protecting groups of the blocked isocyanates and amines is also to be regarded as a disadvantage of this process.

It is the object of the invention to address these disadvantages of the prior art the technology to avoid and to create a binder mixture for the production of Coatings with excellent technical properties result. With the binder mixture according to the invention should the environmental impact during the application of the ent- ^ speaking coating agents are reduced.

This task is performed with a binder mixture

initially mentioned type solved according to the invention by 15

that they consist of the components

A) an organic resin with primary and / or secondary and optionally also additional tertiary ones

Amino groups and
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B) a crosslinking agent based on an organic compound containing at least 2 carbalkoxymethyl ester groups contains, consists.

In addition to components A and B, the binder mixture advantageously contains pigments as components C, Fillers, crosslinking catalysts, corrosion protection inhibitors and other paint auxiliaries.

The proportion of component A 50 is advantageously 95% by weight and that of component B is 5-50% by weight, the sum of components A and B being 100 % .

The carbalkoxy methyl ester groups react during the baking process of component B with the primary and / or secondary amino groups of the component A to form an amide bond. The basic stick

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The material of the amino group of the resin of component A is thus baked into a pH-neutral amide nitrogen Film transferred. The burned-in film therefore contains fewer basic imperfections. The crosslinking mechanism is in principle in the following reaction scheme described:

R - NH ₂ + R ¹ - 0 - C - CH ₂ - 0 - C - R "

ti Il

ο ο

ι.

ι ^ Τ, optionally catalyst R - NH - C - R "+ R ⁽ - 0 - C - CH ₂ - OH

M Il

0 0

Practically no amino groups are split off during stoving, thus reducing exhaust air problems. the 20th

The hydroxyacetic acid esters split off preferably have a boiling point which they have during the stoving process can act advantageously as a flow control agent.

The amide bond formed during stoving works has a very beneficial effect on the adhesion of the film, especially on metal substrates. This also makes the elasticity of the film is increased. This

Cross-linking mechanism requires high resistance 30

of the paint film against solvents, alkalis and salt spray. Form on iron sheet that has not been pretreated the films have very resistant coatings even without corrosion inhibitors.

Component A of the binder mixture advantageously has a number average molecular weight of 500 to 20,000, preferably from 600 to 10,000. The amine equiva-

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weight of component A of the binder mixture is 150 to 7,500 and preferably 200 to 5,000.

Component A is an organic resin with primary and / or secondary amino groups. If necessary, can tertiary amino groups may also be present.

Introducing the primary and / or secondary amino groups into the organic resin to produce the component A is preferably carried out by reacting a polyamine and / or one containing amino and / or hydroxyl groups Ketimines with resins containing at least one, preferably contain at least two epoxy groups or isocyanate groups per molecule.

The component A can also be obtained by other addition reactions, e.g. by esterification or Amidation of compounds carrying primary and / or secondary amino groups with groups suitable for this purpose

holding resins.

Resins containing epoxy groups have proven to be particularly suitable for the production of component A preferably terminal epoxy groups from the group the polyglycidyl ethers, polyglycidyl esters and polyglycidyl amines.

Other advantageously suitable resins containing epoxy groups

are copolymers of acrylic acid and / or methacrylic-30

acid glycidyl ester or another, a glycidyl group-bearing, olefinically unsaturated, polymerizable Compound with alkyl and / or hydroxyalkyl esters of acrylic and / or methacrylic acid, and / or vinyl compounds such as styrene, vinyl toluene or vinyl carbazole.

Another preferably suitable group of resins are partially epoxidized Polybutadiene oils.

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Polyglycidyl ethers in the context of this invention are preferably those polyglycidyl ethers of the general formula

CH_-CR ¹ -R ² - / -ORO-CH «-CR ¹ -R ² - I -0-R-0-R ² -CR ¹ -CH _o

K  ^ [ J V

OH

R * -

R ^

R ¹ = H or

η + 1

R ² -

3 R = R, halogen and preferably H

η = 0 to 5

Understood.

The polyglycidyl ethers of the general formula given have a number average molecular weight of about 340 to 5000 and accordingly an epoxy equivalent weight of up to 2,500. The epoxy resins can also be hydrogenated or can be used partially hydrogenated. For controlling the film properties some of the reactive groups of the epoxy resin can be reacted with other compounds, The following are available for this:

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a) Compounds containing carboxyl groups such as saturated or unsaturated monocarboxylic acids (e.g. benzoic acid, Linseed oil fatty acid, 2-ethylhexyl acid, versatic acid, aliphatic, cycloaliphatic and / or aromatic ^ table dicarboxylic acids of various chain lengths

(for example adipic acid, sebacic acid, isophthalic acid or dimeric fatty acids), hydroxyalkylcarboxylic acids (for example lactic acid, dimethylolpropionic acid) and polyesters containing carboxyl groups or
10

b) Amino group-containing compounds such as diethylamine or ethylhexylamine or diamines with secondary amino groups, such as Ν, Ν'-dialkylenediamine such as dimethylethylenediamine, N ₅ N'-dialkylpolyoxialkyleneamine

such as M, N ¹ -Dirnethyl-polyoxipropylenediamine, cyanoalkylated alkylenediamines such as bis-Ν, Ν'-cyanoethylethyldiamine, cyanoalkylated polyoxialkyleneamines such as bis-N, N-cyanoethylpolyoxypropylenediamine, polyaminoamides such as Versamide or the reaction product of one mole of diamino-

hexane with two moles of monoglycidyl ether or monoglycidyl ester, especially glycidyl ester of C-branched fatty acids like the versatic acid, or

c) compounds containing hydroxyl groups such as neopentyl glycol, bisethoxylated neopentyl glycol, neopentyl glycol hydroxypivalate, Dimethylhydantoin-Ν, Ν'-diethanol, 1.6-hexanediol, 2.5-hexanediol, butene-2-diol-1.4-, Butyne-2-diol-1.4 ,. Hexyne-3-diol-2.5 or

other alkynediols, 1 ^ -Bis-thydroxymethyD-cyclohexane, 30th

1.1-isopropylidene-bis (p-phenoxyl) -2-propanol, trimethylolpropane, Pentaerythritol or amino alcohols such as triethanolamine, methyldiethanolamine or those containing hydroxyl groups Alkyl ketimines such as aminomethylpropane

diol-1,3-methyl-isobutylketimine or tris- (hydroxy-35

methyly-aminomethane-cyclohexane ketimine as well as polyglycol ethers, Polyester polyols, polyether polyols, polyoaprolactone polyols,

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different functionality and molecular weights.

Instead of polyglycidyl ethers based on bisphenol A.

can also use polyglycidyl ethers based on other reason-5

components such as triglycidyl isocyanurate, heterocyclic diglycidyl compounds or diglycidyl hydantoins are used will.

The polyglycidyl esters are reaction products of, for example, bisglycidyl terephthalate or bisglycidyl isophthalate suitable with e.g. bisphenol A. The epoxy equivalent weight of these products is between 200 to 2 500. To control the film properties, a ., -. Part of the remaining, reactive glycidyl groups with other compounds are implemented. The compounds mentioned above under a, b and c are suitable for this purpose at.

2Q Polyglycidylamines are those containing glycidyl groups Understood resins that can be obtained by introducing glycidyl groups via e.g. epichlorohydrin in NH_-functional Preserves resins.

2g Copolymers of acrylic and / or methacrylic acid glycidyl ester or another, olefinically unsaturated, polymerizable compound bearing a glycidyl group with esters of acrylic and / or methacrylic acid and polymerizable vinyl compounds with a number average molecular weight of 700 to 10,000 and a Have epoxy equivalent weight of 600 to 3,000. The acrylic acid esters with C ₀ to C ₀ alcohols and the methacrylic acid esters with are preferred

C- O

C ₁ to C alcohols. The copolymers can contain other monomers such as hydroxyalkyl (meth) acrylate or (meth) acrylamide. The copolymerization takes place in a well-known manner by solution, suspension or emulsion polymerization with the addition of free-radical initiators

such as peroxides, hydroperoxides, peresters or thermolabile Azo compounds and, if appropriate, molecular weight regulators.

Partially epoxidized polybutadiene oils are reaction products that result from the reaction of commercially available borrowed polybutadiene oils can be obtained with peracids or organic acid-HpOp mixtures. The representation method is described e.g. in Chemiker-Zeitung 95, 857f (1971).

The resins containing epoxy groups are made with polyamines and / or one containing amino and / or hydroxyl groups Ketimine implemented. If the attachment of the primary and 5th

If the compounds carrying secondary amino groups are carried out in the form of their ketimines, the reaction conditions must be such that no substances which decompose the ketimines remain in the reaction product. The preferred ketimines are reaction products of ketones and hydroxyl or sec. Alkylamines or alkyldiamines containing amino groups with the general structure R-NH-R ¹ -Nh "or HO-R-NHp. The ketimines have the following structure, for example:

X-N = C X-N-C

HO-CH ^ ^ R HO-CH ₀ -XN R

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where mean:

X = - (CR ₂ ) _n -

R = -H, -R 5 ¹

R '= -CH ₀ , -CI m 2m + 1,

U = -R, -YY = -XN = C, -X-OH, -R 'or -CH ₂ -CH-CH ₂ -OZR ¹

R OH

Z »^ CQ, -X 15th

η = 1 -

m = 1 -

The ones used to react with the primary amino groups Ketones are generally aliphatic ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, Ethyl n-propyl ketone and cycloaliphatic ketones such as Cyclopentanone and cyclohexanone. The preferred aminos

alkylamines and alkanolamines are mainly diethylenetriamine, N-methyl-ethylenediamine, N-methylpropylenediamine, N-aminoethyl-piperazine, 2-aminoethanol, l-aminopropanol-2, l-aminopropanol-3, 2-amino-2-methyl-

propanol-1,3-amino-2,2-dimethyl-propanol-1,3,5-diamino-30

pentanol-3 or N- (2-aminoethyl) -N- (2-hydroxyethyl) ethylenediamine.

The exothermic addition of the aminokeiimines described above to the epoxy groups of the base resin of the binder component A is generally carried out at room temperature. The reaction is frequently ended at temperatures between 50 and 125 ° C. for complete implementation.

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* The addition of the hydroxyketimines to the epoxy groups of the base resin of the binder component A is usually carried out in the same temperature range, but the Use of a basic catalyst such as N, N-dimethylbenzylamine or a Friedel-Crafts catalyst like tin-II-chloride advisable.

As a base resin of the binder component A can also Base resins with at least 2 isocyanate groups can be used. Preferred resins containing isocyanate groups are higher-functional polyisocyanates that are produced by trimerization or oligomerization from diisocyanates or polyisocyanates and polyfunctional OH or NH groups containing compounds are shown. Typical

¹ ^ isocyanates are toluene diisocyanates are toluene diisocyanate, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane and l-isocyanato-methyl-3-isocyanato-1, 5,5-trimethylcyclohexane. Furthermore you can

^ΔΚ * isocyanate-containing prepolymers based on polyglycol ethers, polyester polyols, polyether polyols, polycaprolactone polyols or polyaminoamides can be used with advantage.

The binder component B, the crosslinking agent, is a compound which has at least 2 carbalkoxymethyl ester groups contains. The crosslinking agent can be a low molecular weight compound or an appropriately substituted one Be resin. Used to esterify an alcohol without

If a carbalkoxy group is used, but monoalcohols such as methyl, ethyl or butyl alcohol, it works Amidation reaction is too slow.

In this case, the crosslinking rate is too low, and the stoved film is insufficient against solvents resistant. These disadvantages are circumvented if, according to the invention, carbalkoxymethyl ester for amidie

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tion reaction can be used. The compounds that form the locking agent are preferably polyester resins, however, it is also possible to use other compounds which contain free carboxyl groups on which the carbalkoxymethyl groups can be attached. These compounds can furthermore be primary, secondary or contain tertiary nitrogen atoms that are acidic too are protonizing. So that the resins become water-soluble, they can also be mixed with ammonium groups or with sulfide / Acid or phosphine / acid mixtures can be modified.

Poly (carbalkoxymethyl) esters are preferred as the amidation component used by polycarboxylic acids.

This includes among others

Bis (carbalkoxymethyl) azelate

Bis (carbalkoxymethyl) sebacate
Bis (carbalkoxymethyl) adipate
Bis (carbalkoxymethyl) decanate

Bis (carbalkoxymethyl) terephthalate 20

Polyfunctional crosslinkers can also be advantageously represented in the following way. First are equivalents Portions of a dicarboxylic acid anhydride (phthalic anhydride, hexahydrophthalic anhydride, trimellitic acid-25

anhydride, succinic anhydride) with a polyol (glycerine, trimethylolpropane, pentaerythritol, dipentaerythritol) Temperatures below 145 C implemented. The acidic intermediate produced is then processed according to generally known,

Methods not related to this invention for the 30th

Carbalkoxymethylesters implemented.

Component B is advantageously a polyacrylate resin made from the following monomers:

a) 10-50% by weight of acrylic acid alkyl esters with 1 to 18

Carbon atoms in the alkyl radical and / or methacrylic acid ester with 2 to

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18 carbon atoms in the alkyl radical,

b) 0 - 60 % by weight of methyl methacrylate,

c) 0-35% by weight of styrene, ol-methylstyrene, o- and / or

p-chlorostyrene, p-tert.-butylstyrene, Vinyl toluene and / or vinyl carbazole and

d) 2-65% by weight carbalkoxymethyl methacrylate and / or

Carbalkoxymethyl acrylate or another carbalkoxymethyl ester group containing olefinic, unsaturated th polymerizable compound,

the sum of the components a, b, c and 100 % .

The binder mixture according to the invention can be fine-2Q in part, solid form or dissolved in an organic solvent.

For electrocoating, it is necessary that the binder mixture after protonation with Acid is in the form of an aqueous solution or dispersion. The water solubility of the binder component and / or the crosslinker component is neutralized by the primary, secondary contained in them and / or tertiary amino groups with acids.

Suitable acids are in particular organic acids, but it can also, for example, hydrochloric acid or Phosphoric acid can be used. The amino groups with formic acid, acetic acid, malonic acid, Lactic acid or citric acid neutralized.

The acids mentioned can also be used when introducing the solubilizing groups for the Binder component and / or the crosslinking component

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by adding an ammonium group or the salt of a sulfide / acid or phosphinic acid mixture to the Binder or the crosslinker takes place.

The degree of neutralization of the solubilizing groups, based on these groups, is between 0.2 and 1.0 Equivalents and preferably between 0.25 to 0.6 equivalents of acid.

The neutralization can be carried out in the following ways. The acid is combined in water, if appropriate with dispersing aid, and the resin solution is at room temperature or optionally at increased p. Temperatures stirred into the water. The acid can but 'can also be added directly to the resin solution. The neutralized resin solution can now be stirred into the water If necessary, the water can also be slowly incorporated into the resin solution.

The dispersion can contain up to 20% organic solvents to control its viscosity, the deposition voltage and the flow. Does the approach contain too much or even for

2g the properties of harmful solvents, so can they are distilled out of the resin solution before dispersing or they are distilled from the aqueous solution Dispersion from. The lowest possible proportion of organic is advantageous for the sum of all properties Solvents.

The solid body of a deposition bath, which with the inventive Dispersion is made up, is 7-35 parts by weight, but preferably 12-25 parts by weight. The pH of the deposition bath is between 4 and 8, but preferably between 5 and 7.5. As anodes of the deposition bath non-corrosive steel anodes or graphite anodes are used. The temperature of the bath approach should

3 Ί 457 H.

between 15 to 35 ° C preferred are 20 to 30 ⁰ C. The deposition time and tension are chosen so that the desired layer thickness is achieved.

After the deposition, the coated object is rinsed off and is ready for baking.

Regardless of the application method based on the binder mixture according to the invention produced Coating agent, the crosslinking of the paint film takes place during stoving at temperatures from 130 to 200 ° C. over a period of 10-60 minutes is preferred at 150 to 180 ° C for 15-30 minutes.

The amidation reaction can be carried out by suitable catalysts can still be accelerated. Ammonium compounds such as benzyltrimethylammonium hydroxide are particularly suitable for this purpose, Benzyl trimethyl ammonium chloride, trimethyl cetyl ammonium bromide or tetraammonium iodide and organic tin compounds such as dibutyltin dilaurate and iron (III) acetylacetonate, Zinc acetate, zinc 2-ethylhexoate, cobalt naphthenate, lead acetate or butyl titanate.

",. The pigmentation is done in a well known manner. Here the pigments and the usual additives such as fillers, corrosion inhibitors and antifoam agents be ground in one of the two binder components. As a grinding unit, e.g. sand

QQ mills, ball mills or three-roll mills can be used.-The completion of the lacquer can be done, as is well known.

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The individual components A and B and, if appropriate, component C can be mixed in the form of their concentrated solutions and dispersed together. However, it is also possible for the components A and B separately, the pigments in A or B are triturated to disperse, and the dispersion of the individual components in the required ratio to mix IQ loan.

The invention also relates to a method for producing coatings by applying a coating agent onto a substrate in the form of a film by baking, the coating agent containing a binder mixture, which is characterized in that the mixture of the components

A) an organic resin with primary and / or secondary and optionally also additional tertiary amino groups and

B) a crosslinking agent based on an organic compound containing at least 2 carbalkoxymethyl ester groups contains, consists.

Advantageous refinements of the method according to the invention emerge from subclaims 11 to 20.

The invention further relates to the use of a binder mixture for the production of coatings, which is characterized in that the mixture of the components

A) an organic resin with primary and / or secondary and optionally also additional tertiary amino groups and

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Vf

B) a crosslinking agent based on an organic compound containing at least 2 carbalkoxymethyl ester groups contains, consists.

Advantageous embodiments of the use according to the invention emerge from subclaims 22 to

In the following the invention is explained in more detail _{with reference to embodiments 0 examples.}

example 1

Representation of a tetrafunctional crosslinking agent

109 g of pentaerythritol are mixed with 474 g of phthalic anhydride in a 4-necked flask equipped with a reflux condenser, stirrer, internal thermometer and gas inlet are mixed and heated to 140 ° C. under nitrogen. The reaction then proceeds exothermic and is kept at 160 ° C. by cooling. When the acid number is 305, the batch is brought to room temperature cooled and mixed with 300 g of acetone. Then 81 g of triethylamine are added and 98 g are added dropwise Ethyl chloroacetate. This is followed by heating to reflux temperature. The temperature is maintained for 4 hours and then lets cool the approach. After 12 hours, the triethylammonium chloride formed is filtered off. The acetone is removed from the filtrate on a rotary evaporator.

Example 2

Representation of a polyfunctional crosslinker

142 g trimethylol propane, 723 g caprolactone and 600 g

Methyl isobutyl ketone are placed in a reaction vessel and heated to reflux temperature. To 609 g of trimellitic anhydride are added for 6 hours. When the acid number is 228, you cool down

50 ^° C., adds a further 600 g of methyl isobutyl ketone to 30

and 641 g of triethylamine are slowly added dropwise. By cooling

the temperature is kept at 60 ^° C. 685 g of methyl chloroacetate are then added. The reaction is carried out at 60 ° C. for 4 hours. It is then cooled to room temperature and the salt formed is filtered off
70 %.

is carried out for 4 hours at 60 ° C. Then cools

Salt off. The solid body of the crosslinking resin is included

4 y

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Example 3

Representation of a polyfunctional crosslinking agent based on a polyacrylate resin 5

560 g of xylene are placed in a 5 l reactor under nitrogen and heated to reflux temperature. Within of 4.5 hours, a monomer mixture of 1,400 g Methyl methacrylate, 560 g carbethoxymethyl methacrylate, 840 g ethylene hexyl methacrylate and 14 g dodecyl mercaptane added dropwise. At the same time, 140 g of tert-butyl peroctoate in 200 g of xylene are metered in. Then until Achieving a constant viscosity of 4.0 dPa.s, 50% in xylene, post-polymerized. After that, the Solids of 70% adjusted with xylene.

The number average molecular weight, measured by gel permeation chromatography against a polystyrene standard, is 2,100.
20th

Example 4

Representation of a dispersion of component A.

In a 4 l reactor, 1,188 parts by weight of bis (4-hydroxycyclohexyl) -2,2-propan-bisglycidyl ether, 308 parts by weight of bisphenol A, 675 parts by weight of polytetrahydrofuran (molecular weight 1,000) and 189 parts by weight of xylene. 5 parts by weight of dimethylbenzylamine are used as the catalyst added. The mixture is heated to 170 ° C. and held at this temperature for half an hour. It is then cooled to 136 ° G and a further 10 parts by weight of dimethylbenzylamine are added * The temperature is maintained until an epoxy equivalent weight of 1,500 is reached. It is then cooled to 85 ° C. and added 725 parts by weight of the 70% strength crosslinker solution (Example 2). The temperature is allowed to rise again to 85.degree

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and adds 515 parts by weight of a 70% strength solution of 1 mole of diethylenetriamine and 2 moles of methyl isobutyl ketone. The approach heats up here. The temperature is kept between 95 and 100 ^° C. for 60 minutes by external cooling.

In the meantime, a mixture of 4,070 parts by weight of deionized water, 81 parts by weight of acetic acid and 21 parts by weight of a commercially available defoamer has been prepared. The resin described above is then dispersed in this mixture. The dispersion has a solids content of 40% and a degree of neutralization of the amine groups of 33 %. After one hour, a further 970 parts by weight of water are added in order to set a solids content of 35%. ■

Example 5

2Q Preparation of a pigment paste containing component A for an electro-dip bath

The approach described in Example 4 for the preparation of an organic resin is repeated, but before

stopped before dispersion and worked up as described below. For this purpose, a water-acetic acid mixture (162 g acetic acid + 64 g water) is added to the batch in order to bring about 100% neutralization of the amine groups. A solids content of 50 % is then set with deionized water.

The pigment paste is made from the following components

2,380 g of 50% strength resin solution
1,670 g of coal dust

200 g lead silicate
1,200 g of deionized water

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The starting materials are comminuted to a Hegman fineness of 6 to 7 in a grinding unit. Then more deionized water is added to achieve the desired consistency. The pigment paste has a solids content of 56.1%, a resin content of 21.8 % and a pigment solids content of 34.3%. The paste has excellent thermal stability on storage.

Example 6
10

Preparation of an electro-dip bath

287.5 g of the binder described in Example 4

and 178 g of the pigment paste 15 described in Example 5

2,434.5 g of deionized water are added.

The solids content of the deposition bath resulting from the mixture is 16%. The pH is 7.5%. The breakdown voltage of the bath is 370 to 380 V. Steel sheets treated with zinc phosphate become ₀

at a bath temperature of 25 C and 300 volts 120 Seconds coated. This results in continuous films which are stoved at 160 ° C. after 20 minutes resulted in a smooth, well-adhering layer of 30 μm.

Example 7

Representation of a dispersion of component A.

In a 6 l reactor, 3 38.0 g of partially epoxidized oU

Polybutadiene (mol wt 2600, 4.8 wt -..% Of epoxide) with 1 453 g of a 90% solution of the ketimine of mono-isopropanolamine and methyl ethyl ketone in methyl ethyl ketone was added and 32.5 g of phenol was added as a catalyst _oc . The mixture is heated to 160 ⁰ C and held at this temperature until no more epoxide is detected. Then you cool the approach

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to 90 ^° C. and a solution of the crosslinker from Example 3 adjusted to 70% solids is added. The crosslinker solution is mixed in for 15 minutes. The batch is then dispersed in a mixture of 6,210 g of deionized water, 281 g of lactic acid and 55 g of a commercially available defoamer. The dispersion has a solids content of 40% and a degree of neutralization of the amine groups of 40 % .

Example 8

Representation of a pigment paste

146 g of a reaction product of an epoxy resin with

an epoxy equivalent weight of 890 and diethanolamine lactic acid salt are presented with 199 g of deionized water. For this purpose, 200 g of Ti 0.1, 48 g of extender are added Based on aluminum silicate, 11 g lead silicate and 3 g carbon black given. The starting components are in a grinding

crushed aggregate to a Hegman fineness of 5-7. A further 102 g of deionized water are then added in order to achieve the desired paste consistency. the gray pigment paste is very stable in storage.

Example 9

Preparation of an electro-dip bath

500 parts by weight of the binding 30 described in Example 7

Medium dispersion and 196 parts by weight of the pigment paste described in Example 8 are mixed with 804 parts by weight of deionized water. The non-volatile content of the bath batch is 20 %. This deposition bath has a pH of 6.2. Films, which are deposited on zinc phosphated sheet metal in the course of 2 minutes at 300 volts and baked for 30 minutes at 170 ⁰ C, exhibit a smooth, hard surface not yellowed. The film thickness is 25 µm. Liability

on the sheets is excellent.

10

15th

20th

25 30 35

Claims (33)

Claims ο 1. Thermosetting binder mixture based on organic resins, characterized in that it consists of the Components A) an organic resin with primary and / or secondary and optionally also additional tertiary ones Amino groups and B) a crosslinking agent based on an organic, c see compound containing at least 2 carbalkoxymethyl groups contains, consists. 2. Binder mixture according to claim 1, characterized in that in addition to components A and 2Q B as component C pigments, fillers, crosslinking catalysts, corrosion inhibitors and others '. Contains paint auxiliaries. 3. Binder mixture according to claim 1 and 2, characterized in that the proportion of component A is 50-95% by weight and that of component B is 5-50% by weight, the sum of components A and B being 100 % amounts to. 4. Binder mixture according to claim 1 to 3, characterized characterized in that component A is a number average. Has a molecular weight of 500 to 20,000. 31457H 5. Binder mixture according to claim 1 to 4, characterized characterized in that component B has a number average molecular weight of 200-10,000. 6. Binder mixture according to claim 1 to 5, characterized in that component B is a polyacrylate resin is made up of the following monomers: a) 10-50% by weight of acrylic acid alkyl esters with 1 to 18 carbon atoms in the alkyl radical and / or methacrylic acid ester with 2 to 18 carbon atoms in the alkyl radical, b) 0-60% by weight of methyl methacrylate, c) 0-35 wt .-% styrene, oi, -Methy 1 styrene, o- and / or p-chlorostyrene, p-tert.-butylstyrene, Vinyl toluene and / or vinyl carbazole and d) 2-65% by weight of acrylic acid and / or methacrylic acid carbalkoxymethyl ester or another carbalkoxymethyl ester-25 group-containing, olefinic, unsaturated, polymerizable compound, the sum of components a, b, c and d being 100% amounts to. 7. Binder mixture according to claim 1 to 6, characterized in that it is in finely divided, solid Form. 8. Binder mixture according to claim 1 to 6, characterized characterized as being dissolved in an organic Solvent is present. 9. binder mixture according to claim 1 to 6, characterized characterized in that, after protonation with acid, it is in the form of an aqueous solution or dispersion is present.
5 10. A method for producing coatings by applying a coating agent to a substrate in Form of a film and subsequent curing of the film by baking, the coating agent contains a binder mixture, characterized in that the mixture of the components A) an organic resin with primary and / or secondary and optionally also additional tertiary ary amino groups and B) a crosslinking agent based on an organic compound containing at least 2 carbalkoxymethyl ester contains groups.
20th 11. The method according to claim 10, characterized in that the mixture in addition to components A and B as component C pigments, fillers, crosslinking agents - catalysts, corrosion inhibitors and more «; 25th Contains paint auxiliaries. 12. The method according to claim 10 and 11, characterized in that the proportion of component A 50-95 % By weight and that of component B 5-50% by weight is 30 gen, where the sum of components A and B is 100%. 13. The method according to claim 10 to 12, characterized in that that component A is a number average Has a molecular weight of 500-20,000. 3U57U 14. The method according to claim 10 to 13, characterized in that that component B has a number average molecular weight of 200-10,000. 15. The method according to claim 10 to 14, characterized in that component B is a polyacrylate resin is made from the following monomers: a) 10-50% by weight of aryl acid alkyl ester with 1 to ¹ ^ 18 carbon atoms in the alkyl radical and / or methacrylic acid esters with 2 to 18 carbon atoms in the alkyl radical, b) 0-60% by weight of methyl methacrylate, c) 0-35% by weight of styrene, Qt -methylstyrene, o- and / or p-chlorostyrene, p-tert.-butylstyrene, Vinyl toluene and / or vinyl carbazole , and d) 2-65% by weight of acrylic acid and / or methacrylic acid carbalkoxymethyl ester or one other carbalkoxymethyl ester groups containing, olefinically unsaturated, polymerizable compound, the sum of the components a, b, c and d being 100 % . 16. The method according to claim 10 to 15, characterized in that the coating agent in finely divided,
solid form. 17. The method according to claim 16, characterized in that 35 that the application of the coating agent by a electrostatic powder spraying device takes place. 31457H ^p 18. The method according to claim 10 to 15, characterized in that the binder mixture dissolved in one organic solvent is present. 19. The method according to claim 18, characterized in, that the coating agent is applied by spraying, dipping, flooding, rolling, knife coating or the like. 20. The method according to claim 10 to 15, characterized in that that an electrically conductive substrate in an aqueous bath which is at least partially acidified neutralized coating agent, which optionally p. additionally contains organic solvents, immersed and is connected as a cathode, the film is deposited on the substrate by means of direct current the substrate is removed from the bath and the film is cured by baking. 21. Use of a binder mixture for the production of coatings, characterized in that the mixture of the components ng A) an organic resin with primary and / or secondary and optionally also additional tertiary amino groups and B) a crosslinking agent based on an organic Compound containing at least 2 carbalkoxymethyl ester groups. 22. Use according to claim 21, characterized in that that the mixture in addition to components A and B as component C pigments, fillers, crosslinking catalysts, Corrosion protection inhibitors and contains other paint auxiliaries. 23. Use according to claim 21 and 22, characterized in that that the proportion of component A 50 is 95% by weight and that of component B is 5 - 50% by weight, where the sum of components A and B is 100%. 24. Use according to claim 21 to 23, characterized in that that component A has a number average molecular weight of 500-20,000. 25. Use according to claim 21 to 24, characterized in that that component B has a number average molecular weight of 200-10,000. 26. Use according to claim 21 to 24, characterized in that that component B is a polyacrylic resin made from the following monomers: a) 10 - 50 wt -.% acrylic acid alkyl ester having 1 to 18 20 Carbon atoms in the alkyl radical and / or methacrylic acid esters with 2 to 18 carbon atoms in the alkyl radical, b) 0-60% by weight of methyl methacrylate, 25 c) 0-35% by weight styrene, 0 £ -methylstyrene, ο- and / or p-chlorostyrene, p-tert-butylstyrene, vinyltoluene and / or vinyl-O ₀ carbazole and d) 2-65% by weight of acrylic acid and / or methacrylic acid carbalkoxymethyl ester or another carbalkoxymethyl ester group OK pen containing, olefinic, unge saturated polymerizable compound, v / obei the sum of components a, b, c and d is 100 % . 27. Use according to claim 21 to 26, characterized in that the binder mixture in finely divided, solid form. 28. Use of the binder mixture according to claim 27 for powder coatings. 29. Use according to claim 21 to 25, characterized in that the binder mixture is dissolved in one organic solvent is present. 30. Use of the binder mixture according to claim 29 for stoving enamels. 31. Use according to claim 21 to 25, characterized in that the binder mixture after protonation with acid is in the form of an aqueous solution or dispersion. 32. Use of the binder mixture according to claim for cathodic electrocoating. 33. Use of the binder mixture according to claim 27 in finely divided, solid form for aqueous powder-25 Slurries.